CN104677925A - Method for measuring ratio of each iron oxide in mixture - Google Patents
Method for measuring ratio of each iron oxide in mixture Download PDFInfo
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- CN104677925A CN104677925A CN201510125298.3A CN201510125298A CN104677925A CN 104677925 A CN104677925 A CN 104677925A CN 201510125298 A CN201510125298 A CN 201510125298A CN 104677925 A CN104677925 A CN 104677925A
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Abstract
The invention provides a method for measuring a ratio of each iron oxide in a mixture. The method comprises the following steps: taking 5-15mg of a to-be-measured sample, grinding the sample into powder, and uniformly mixing; adding the ground powder sample into a transmission type Mossbauer spectroscope sample chamber, and measuring the relationship between gamma ray counting of an absorber and the modulation energy, namely Doppler velocity; and performing spectrum recognition and peak spectrum fitting, finally exporting the fitting result, and reading the ratio of the iron oxide of each structure in the sample. According to the method disclosed by the invention, the problem that the ratios of various iron oxides in the mixture cannot be measured in the conventional method is solved, and oxide skin in a steam pipeline is taken as an example, if the ratio of each iron oxide in the oxide skin is unknown, the generation amount and distribution condition of the oxide skin in the pipeline are difficultly accurately judged according to magnetic parameters, so that a proper maintenance and check plan is difficultly made, possible hazards formed by accumulation of the oxide skin in the pipeline are reduced. The method disclosed by the invention belongs to the fields of component measurement and analysis.
Description
Technical field
The present invention relates to a kind of assay method of ferriferous oxide proportion, be specifically related to the method measuring variety classes, structural iron oxide proportion in potpourri.
Background technology
At present, method for measuring is not carried out to ferriferous oxide content/ratio various in potpourri in the industry, and in production application, measure various ferriferous oxide content in potpourri and there is larger use value.
With Super304H more representative in Novel austenitic heat-resistance steel, Super304H has become the main material of domestic and international super (super-) critical (USC) thermal power unit boiler reheater and superheater, the serviceability temperature of the type steel is higher, but the pipeline of steam side meeting accelerated oxidation under water vapor acting in operational process, oxide skin time long after oxidation will have certain thickness, due to differing greatly of linear expansion coefficient between oxide skin and austenite stainless steel matrix and elastic modulus, consequent thermal stress causes oxide skin to peel off from inner-walls of duct, the oxide skin that pipe interior peels off can flow at boiler internal along with steam, the oxide skin of flowing comparatively can stop formation further accumulation in many places in the pipe bent position of pipeline or pipeline oxidization skin,
These oxide skins of peeling off accumulation can cause following problem:
Cause boiler heating surface pipeline to block, cause steam to circulate not smooth, heat cannot be taken out of in time and cause metal heated of boiler local overheating occurs, and causes booster;
The oxide skin of peeling off is brought steam turbine into by steam and is damaged Turbine Flow Path, if lower steam turbine efficiency to occur the accumulation of peeling off oxide skin between steam turbine throttle spool and valve seat, steam turbine main inlet throttle-stop valve is very easily caused to occur bite, when finally causing load rejection, throttle is not closed completely, cause steam turbine to exceed the speed limit, the oxide skin of peeling off in addition causes the decline of Steam-water Quality in unit.
Therefore needing by detecting after scale spallation, the distribution situation of the oxide skin of understanding pipe interior, formulating maintenance and planning with investigation, may endangering of the formation that minimizing oxide skin is piled up in the duct.Oxide skin detection method common at present mainly contains:
Ray detection method: ray detection utilizes gamma-ray penetration capacity, makes oxide skin shading on egative film, by the image on radiographic film then can intuitive judgment pipe interior oxide skin pile up situation, testing result is reliably directly perceived.But to expend time in and checkout equipment is not easy to some places within boiler and detects, so be not suitable for the Real-Time Monitoring of boiler tubing because such detects to compare.
Pipe cutting detection method: pipe cutting detects mainly for having abnormal pipe to carry out investigating and processing, and this method is generally applicable to the pipeline that oxide skin blocking exceedes interface 30%.This inspection method is very directly perceived but cost is also very large, and have in auxiliary detection means situation, the method is the investigation and method for cleaning insured the most.
Thus the way that the most of power plant of real-time detection of the accumulation situation of pipe interior oxide skin all uses magnetics to detect carrys out auxiliary pipe cutting cleaning work.It is the difference on magnetic performance according to oxide skin and heat-resisting steel that magnetics detects, and uses checkout equipment to obtain the magnetics parameter of a certain segment pipe, then according to rich experience, judges that the oxide skin of pipe interior generates and the situation of accumulation.Designed by this method, equipment is comparatively convenient, conveniently uses in boiler everywhere pipeline.Thus this method is promoted well, but the method needs operating personnel to have experience well, because the oxide in oxide skin is various, be wherein three kinds is FeO, Fe respectively
2o
3, Fe
3o
4, tri-iron tetroxide structure is comparatively special, and it is inverse spinel structure, and Fe3+ ion is in tetrahedral site, Fe3+ and the Fe2+ ion of equal number is positioned at octahedron in addition, is A, B two kinds.When A, B two kinds of different structures are at Fe
3o
4when proportion is different, tri-iron tetroxide will present different magnetic performances.There is ferromagnetic Fe O and Fe
2o
3there is paramagnetism (α does not have magnetic γ type to have magnetic), calculated by the unpaired electron number of the two, Fe
2o
3paramagnetism stronger.The magnetic performance of various oxide is certainly also different, thus the various oxide ratios of the oxide skin of the pipe interior of different duration is used to change to some extent, the magnetic performance of the oxide skin of thus piling up not is well-determined, thus the oxide ratios of various iron in oxide skin is studied, for judging that the content tool of pipe interior accumulation oxide skin is of great significance.And the domestic detect delay for pipe interior accumulation oxide mainly concentrates on detection means and instrument development at present, the ratio research of the inner various oxide of oxide skin there is no report, and this problem is ignored by most institute.
Summary of the invention
The object of the invention is to: a kind of method measuring each ferriferous oxide proportion in potpourri is provided, to solve the problem that existing method cannot measure the ratio of various ferriferous oxide in potpourri, for jet chimney internal oxidition skin, if do not know the ratio shared by each ferriferous oxide in oxide skin, the generation and the distribution situation that accurately judge pipeline internal oxidition skin is difficult to according to magnetics parameter, thus be difficult to formulate appropriate maintenance and investigate plan, what formed to reduce oxide skin to pile up in the duct may endanger.
The solution of the present invention is as follows: a kind of method measuring each ferriferous oxide proportion in potpourri, comprises the steps:
Step one: get testing sample 5-15mg, is ground to Powdered and is mixed;
Step 2: ground powdered samples is put into transmission-type mossbauer spectrometer sample chamber, the acceleration such as radioactive source is adjusted to, after the velocity range choosing radioactive source and energy of γ ray, measure through absorber gamma ray counting and modulation energy namely with the relation of doppler velocity;
Step 3: read sample Mo&4&ssbauer spectrum determination data, by sample tests data importing Recoil software, reads sample Mo&4&ssbauer spectrum, and the oxide kind of bind profile wire shaped and each iron judges the oxide kind number of iron in sample;
Step 4: peak spectrum matching: the meticulous field value of iron atom in the oxide of the iron that may exist in sample is imported in Recoil software, matching is carried out to the Mo&4&ssbauer spectrum of sample, the spectral line obtained when matching with record spectral line error amount below 5%, then matching completes;
Step 5: ratio calculates; Fitting result is derived, reads the ratio that the ferriferous oxide of various structure is shared in the sample to which.
Preferably, the oxide skin in jet chimney selected by sample, and its sampling procedure is: cut open by the jet chimney piling up oxide skin, pipe interior oxide skin taken out, and carries out sampling grinding after mixing again;
Preferably, the grinding steps of sample: sample is put into mortar and be ground to less than 50 microns Powdered;
Preferably, the pipe cutting place of above-mentioned jet chimney, apart from oxide skin accumulation place at least 30cm, avoids the iron filings contaminated samples dropped, affects measurement accuracy;
Preferably, in step 2, radioactive source relative absorbance body translational speed scope is-10 to 10mm/s, and ray energy is between 14.0-15.0Kev, can cause the resonance scattering of iron atom core well.
Preferably, in step 5, the meticulous field value of iron atom in different oxide is consulted in " Mossbauer spectroscopy handbook " the inside, choose with step 4 in differentiate the ferro element meticulous field value of composing the same number of quantity in peak, substitute in Recoil software, then carry out matching, the spectral line obtained when matching substantially with record spectral line overlap and error amount in fitting result below 5%, then illustrate that fitting result is ideal, matching completes.
Preferably, in step 6, read fitting result, according to the meticulous field value of the atom of correspondence, determine the structure of the oxide that this iron atom is formed, the detection abundance being multiplied by instrument with thing Phase Proportion shared by each material peak area under spectrum obtains the content of this thing phase; After matching completes, from matching Output rusults site population mono-hurdle, read the ratio that different structure ferriferous oxide is shared in the sample to which.
As shown from the above technical solution the present invention utilize mossbauer spectrometer record gamma ray counting and modulation energy namely with the relation of doppler velocity, the ferriferous oxide proportion of different structure is obtained by matching, for jet chimney internal oxidition skin, after measuring the ratio in oxide skin shared by each ferriferous oxide, generation and the distribution situation of pipeline internal oxidition skin accurately can be judged according to magnetics parameter, thus formulate appropriate maintenance and investigation plan, what minimizing oxide skin was piled up in the duct and formed may endanger;
Meanwhile, the present invention also has following technological merit: first the method is very simple, and experimentation is easy; Second assay method of the present invention has very high accuracy, because mossbauer spectrometer has high resolution, for the γ resonance absorption of 57Fe, gamma energy (E0) is 14.4 kiloelectron-volts, spectral line natural width (Γ) is 4.6 × 10-9 electron volts, Γ/E0 ~ 3.2 × 10-13, resolution reaches 1/1013rd; 3rd is the resonance absorption of the method owing to being particular core (as 57Fe, 119Sn), and mossbauer effect is not subject to the interference of other cores and element; 4th, mossbauer effect is generally less than 2.0 nanometers (being limited within adjacent two, three leafing) by the reach that core external environment affects, and is specially adapted to thin brilliant and amorphous substance.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below the present invention is described in further detail,
Embodiment:
Adopt the Novel austenitic heat-resistance steel Super304H that power plant uses, this steel has very high heat resistance and resistance to corrosion, but this steel after oxidation, the thermal coefficient differences formed between oxide skin and matrix is larger, the thermal expansivity of matrix is the twice of oxide simultaneously, so the spallation problems of oxide skin is comparatively serious in the actual use of power plant.After being taken out by the oxide wherein piled up, utilize Mo&4&ssbauer spectrum to measure to obtain the ferriferous oxide proportion wherein of different structure to it, in running, use oxide skin accumulation content in magnetic detection means testing pipes to offer help.
Concrete steps are as follows:
Step 1: cut open by Super304H pipeline, will wherein oxide skin take out, after mixing, the amount of getting about 10mg puts into the alms bowl of milling of corundum, mills with corundum wooden club, and being milled by sample, it is Powdered to be called, then sample preparation becomes.
Step 2: the sample chamber sample of milling being put into Mossbauer instrument, Mossbauer instrument adopts the aero mode such as transmission, measure through absorber gamma ray counting and modulation energy namely with the relation of doppler velocity; Access speed scope is-10 to 10mm/s, and use 1024 road multichannel analyzer image data, step-length is 10/1024, and ray energy is chosen as 14.4Kev.
Step 3: the Mo&4&ssbauer spectrum taking out oxide skin sample, imports in the Recoil software of specialty, reads sample Mo&4&ssbauer spectrum, according to the oxide of the iron containing 3 kinds of different structures in spectrum peak shape and sample situation judgement sample.
Step 4: show that oxide skin principal ingredient is Fe2O3, Fe3O4 from article data consultation, wherein di-iron trioxide is that paramagnetic material has α-Fe2O3, γ-Fe2O3 two kinds of structures, there is different magnetic performances, and tri-iron tetroxide has tetrahedroid and hexahedron two type, wherein hexahedron has two kinds.The hyperfine field value that article is presented at Fe atom in four kinds of oxides is respectively 511,503,481,454,457.
Step 5: carry out matching by the Fe atom meticulous field value of inquiry in step 4 substitution software dialogue box, repeatedly minimum one group of Select Error value after matching, error amount is less than 5%.
Fitting result in step 5 is read out, known by the parameter list of fitting result.From subordinate list one, in oxide skin α-Fe2O3 altogether ratio be 49.20%, all the other compositions are Fe3O4, and wherein the ratio that exists with A type structure of iron atom is for 15.99%, with Type B structure at Fe3O4 proportion for 34.81%.
Claims (7)
1. measure a method for each ferriferous oxide proportion in potpourri, it is characterized in that, comprise the steps:
Step one: get testing sample 5-15 mg, be ground to Powdered and mix;
Step 2: ground powdered samples is put into transmission-type mossbauer spectrometer sample chamber, the acceleration such as radioactive source is adjusted to, after the velocity range choosing radioactive source and energy of γ ray, measure through absorber gamma ray counting and modulation energy namely with the relation of doppler velocity;
Step 3: read sample Mo&4&ssbauer spectrum determination data, by sample tests data importing Recoil software, reads sample Mo&4&ssbauer spectrum, and the oxide kind of bind profile wire shaped and each iron judges the oxide kind number of iron in sample;
Step 4: peak spectrum matching: the meticulous field value of iron atom in the oxide of the iron that may exist in sample is imported in Recoil software, matching is carried out to the Mo&4&ssbauer spectrum of sample, the spectral line obtained when matching with record spectral line error amount below 5%, then matching completes;
Step 5: ratio calculates; Fitting result is derived, reads the ratio that the ferriferous oxide of various structure is shared in the sample to which.
2. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 1, it is characterized in that: the oxide skin in jet chimney selected by sample, its sampling procedure is: cut open by the jet chimney piling up oxide skin, pipe interior oxide skin is taken out, after mixing, carries out sampling grinding again.
3. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 1 or 2, is characterized in that: the grinding steps of sample: sample is put into mortar and be ground to less than 50 microns Powdered.
4. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 2, is characterized in that: the pipe cutting place of jet chimney is apart from oxide skin accumulation place at least 30cm.
5. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 1, is characterized in that: in step 2, and radioactive source relative absorbance body translational speed scope is-10 to 10mm/s, and ray energy is between 14.0-15.0Kev.
6. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 1, it is characterized in that: in step 4, the meticulous field value of iron atom in different oxide is consulted in " Mossbauer spectroscopy handbook " the inside, choose with step 4 in differentiate the ferro element meticulous field value of composing the same number of quantity in peak, substitute in Recoil software, then carry out matching.
7. a kind of method measuring each ferriferous oxide proportion in potpourri according to claim 1, it is characterized in that: in step 5, read fitting result, according to the meticulous field value of the atom of correspondence, determine the structure of the oxide that this iron atom is formed, the detection abundance being multiplied by instrument with thing Phase Proportion shared by each material peak area under spectrum obtains the content of this thing phase.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108268027A (en) * | 2016-12-30 | 2018-07-10 | 乐视汽车（北京）有限公司 | Driving locus optimization method and optimization system |
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| US20110005353A1 (en) * | 2003-09-09 | 2011-01-13 | Kazuyuki Tohji | Magnetic metal powder and method of producing the powder |
| CN103163081A (en) * | 2011-12-19 | 2013-06-19 | 国民大学校产学协力团 | Mossbauer spectrometer for guiding magnetic field under ultralow temperature through refrigerating machine |
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| CN1472165A (en) * | 2002-07-29 | 2004-02-04 | 北京化工大学 | Method for preparing magnetic ferrite from layered precursor |
| US20110005353A1 (en) * | 2003-09-09 | 2011-01-13 | Kazuyuki Tohji | Magnetic metal powder and method of producing the powder |
| CN103163081A (en) * | 2011-12-19 | 2013-06-19 | 国民大学校产学协力团 | Mossbauer spectrometer for guiding magnetic field under ultralow temperature through refrigerating machine |
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| CN108268027A (en) * | 2016-12-30 | 2018-07-10 | 乐视汽车（北京）有限公司 | Driving locus optimization method and optimization system |
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Address after: 550002 Jiefang Road, Guizhou, No. 251, Applicant after: ELECTRIC POWER RESEARCH INSTITUTE OF GUIZHOU POWER GRID CO., LTD. Address before: 550002 Jiefang Road, Guizhou, No. 251, Applicant before: Guizhou Power Test Institute |
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